Small-angle Neutron Scattering Research Articles

Dynamic mechanical properties and σ precipitates strengthening of a NiCrFeCoMo0.2 high-entropy alloy additively manufactured by selective laser melting

Dynamic mechanical properties of the selected laser melting (SLM)-NiCrFeCoMo0.2 high-entropy alloy (HEA) are further improved by controlling the molten pool structure and the generation of σ-phase precipitation particles. In this study, a split Hopkinson pressure bar (SHPB) was used for testing the dynamical mechanical properties of the quenched SLM-NiCrFeCoMo0.2 HEA specimens. Microstructure and volume fraction of the σ precipitates were characterized by X-ray diffractometry (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), and the small angle neutron scattering (SANS) technique. After heating to 800 ℃, holding for 8 h and water quenching, the molten pool boundary of the SLM-NiCrFeCoMo0.2 HEA disappear, and the ultimate compressive strength and the impact energy of specimens reach 1970 MPa and of 217.45 MJ·m−3, respectively. Due to the segregation of Mo elements in the molten-pool boundary of the as-build SLM-NiCrFeCoMo0.2 HEA, more σ precipitates tend to form at the residual molten pool boundary of the quenched SLM-NiCrFeCoMo0.2 HEA. The σ precipitates play key role in strengthening of the SLM-NiCrFeCoMo0.2 HEA.

Graphical reduction and analysis small-angle neutron scattering program: GRASP.

GRASP is a scientific software application designed for the graphical inspection, reduction and analysis of multidetector data produced by the small-angle neutron scattering (SANS) instruments at the Institut Laue-Langevin and other neutron sources around the world. The first developments of GRASP began more than 20 years ago and were written in MATLAB, allowing rapid development of scientific code, with much of the data handling, matrix manipulation, mathematical tools, user interface and graphical tools integrated at a high level in the underlying MATLAB platform. By their very nature, multidimensional data are often best appreciated in graphical form. GRASP deals with many of the diverse requirements for data reduction and analysis of SANS data using a general set of tools and reduction algorithms suited to 2D multidetector data. A further fundamental architectural inclusion is a third dimension of data manipulation, thereby easily allowing parametric analysis and cross referencing of series data such as composition, kinetic measurements, temperature, magnetic field, angle or time of flight, often considered as a single 'measurement'. This article serves as a reference document for users of the software, and outlines the architecture and strategy of the program. An overview of some of the features, capabilities, peripheral user modules and neutron scattering tools is presented.

Distribution and Mobility of Amines Confined in Porous Silica Supports Assessed via Neutron Scattering, NMR, and MD Simulations: Impacts on CO2 Sorption Kinetics and Capacities.

ConspectusSolid-supported amines are a promising class of CO2 sorbents capable of selectively capturing CO2 from diverse sources. The chemical interactions between the amine groups and CO2 give rise to the formation of strong CO2 adducts, such as alkylammonium carbamates, carbamic acids, and bicarbonates, which enable CO2 capture even at low driving force, such as with ultradilute CO2 streams. Among various solid-supported amine sorbents, oligomeric amines infused into oxide solid supports (noncovalently supported) are widely studied due to their ease of synthesis and low cost. This method allows for the construction of amine-rich sorbents while minimizing problems, such as leaching or evaporation, that occur with supported molecular amines.Researchers have pursued improved sorbents by tuning the physical and chemical properties of solid supports and amine phases. In terms of CO2 uptake, the amine efficiency, or the moles of sorbed CO2 per mole of amine sites, and uptake rate (CO2 capture per unit time) are the most critical factors determining the effectiveness of the material. While structure-property relationships have been developed for different porous oxide supports, the interaction(s) of the amine phase with the solid support, the structure and distribution of the organic phase within the pores, and the mobility of the amine phase within the pores are not well understood. These factors are important, because the kinetics of CO2 sorption, particularly when using the prototypical amine oligomer branched poly(ethylenimine) (PEI), follow an unconventional trend, with rapid initial uptake followed by a very slow, asymptotic approach to equilibrium. This suggests that the uptake of CO2 within such solid-supported amines is mass transfer-limited. Therefore, improving sorption performance can be facilitated by better understanding the amine structure and distribution within the pores.In this context, model solid-supported amine sorbents were constructed from a highly ordered, mesoporous silica SBA-15 support, and an array of techniques was used to probe the soft matter domains within these hybrid materials. The choice of SBA-15 as the model support was based on its ordered arrangement of mesopores with tunable physical and chemical properties, including pore size, particle lengths, and surface chemistries. Branched PEI─the most common amine phase used in solid CO2 sorbents─and its linear, low molecular weight analogue, tetraethylenepentamine (TEPA), were deployed as the amine phases. Neutron scattering (NS), including small angle neutron scattering (SANS) and quasielastic neutron scattering (QENS), alongside solid-state NMR (ssNMR) and molecular dynamics (MD) simulations, was used to elucidate the structure and mobility of the amine phases within the pores of the support. Together, these tools, which have previously not been applied to such materials, provided new information regarding how the amine phases filled the support pores as the loading increased and the mobility of those amine phases. Varying pore surface-amine interactions led to unique trends for amine distributions and mobility; for instance, hydrophilic walls (i.e., attractive to amines) resulted in hampered motions with more intimate coordination to the walls, while amines around hydrophobic walls or walls with grafted chains that interrupt amine-wall coordination showed recovered mobility, with amines being more liberated from the walls. By correlating the structural and dynamic properties with CO2 sorption properties, novel relationships were identified, shedding light on the performance of the amine sorbents, and providing valuable guidance for the design of more effective supported amine sorbents.

Influences of Cu on microstructure and mechanical properties in Fe–Ni–Al ultra-strong maraging steels

Although the influences of Cu on microstructure and mechanical properties have been extensively studied in low-alloy steels, the aging behavior of high-alloy maraging steels with Cu remains elusive. In this work, we systematically investigated the nanoprecipitation behavior and their effects on mechanical properties in Fe–Ni–Al ultra-strong maraging steels by introducing different amounts of Cu. Structural analyses with atom probe tomography (APT), transmission electron microscopy (TEM) and small angle neutron scattering (SANS) indicate that the addition of Cu promotes the precipitation of nanoscale B2–NiAl phases in the Fe–Ni–Al ultra-strong maraging steels. The primarily precipitated Cu-clusters can serve as the nucleation sites for the precipitation of B2–NiAl at the early stage of aging, and then are dissolved into the B2–NiAl nanoprecipitates, which increases the lattice misfit between the B2–NiAl and the matrix and thereby the growth rate of B2–NiAl. As a result, the addition of 0.6 wt% Cu significantly improves the ductility of the Fe–Ni–Al ultra-strong steel without sacrificing strength. With 0.6 wt% Cu added to the Fe–Ni–Al ultra-strong steel, the elongation increased from 3.2% to 8.7% while the strength remained 2.0 GPa, due to the high-density precipitation of Ni(Al, Cu) nanoparticles. The underlying mechanisms for the precipitation behavior and the precipitation strengthening effect were discussed in terms of lattice misfit, Cu segregation and stress field.

Structural characterization of an intrinsically disordered protein complex using integrated small-angle neutron scattering and computing.

Characterizing structural ensembles of intrinsically disordered proteins (IDPs) and intrinsically disordered regions (IDRs) of proteins is essential for studying structure-function relationships. Due to the different neutron scattering lengths of hydrogen and deuterium, selective labeling and contrast matching in small-angle neutron scattering (SANS) becomes an effective tool to study dynamic structures of disordered systems. However, experimental timescales typically capture measurements averaged over multiple conformations, leaving complex SANS data for disentanglement. We hereby demonstrate an integrated method to elucidate the structural ensemble of a complex formed by two IDRs. We use data from both full contrast and contrast matching with residue-specific deuterium labeling SANS experiments, microsecond all-atom molecular dynamics (MD) simulations with four molecular mechanics force fields, and an autoencoder-based deep learning (DL) algorithm. From our combined approach, we show that selective deuteration provides additional information that helps characterize structural ensembles. We find that among the four force fields, a99SB-disp and CHARMM36m show the strongest agreement with SANS and NMR experiments. In addition, our DL algorithm not only complements conventional structural analysis methods but also successfully differentiates NMR and MD structures which are indistinguishable on the free energy surface. Lastly, we present an ensemble that describes experimental SANS and NMR data better than MD ensembles generated by one single force field and reveal three clusters of distinct conformations. Our results demonstrate a new integrated approach for characterizing structural ensembles of IDPs.

Microstructure and mechanical properties of Zr46Cu46Al8 bulk metallic glass after annealing treatment

The crystallization and mechanical behavior of Zr46Cu46Al8 MG is investigated. The small-angle neutron scattering (SANS) and extended X-ray absorption fine structure spectra (EXAFS) is used to reveal the microstructure of Zr46Cu46Al8 bulk metallic glasses (BMG) after isothermal annealing. The incubation period of Zr46Cu46Al8 BMGs was less than 10 min under a variable heating rate. Moreover, a stable crystallization point was determined with nanocrystalline particles sized at 32 Å at the equilibrium using SANS. The Zr and Al atoms shifted outward during crystallization. Thus, the crystallization mechanisms of the Zr46Cu46Al8 BMGs are discussed based on the results of the SANS, X-ray diffraction, EXAFS, and differential scanning calorimetry analyses. The mechanical properties of the BMG and its composites were investigated using a nanoindentation test.

The importance of pore-fracture connectivity in overmature marine shale for methane occurrence and transportation

Pore-fracture connectivity is a critical factor in gas occurrence and transportation in shale plays. To investigate the limiting factors of multiscale pore-fracture connectivity, which might control methane occurrence and transportation in shale reservoirs, small-angle neutron scattering (SANS) under vacuum and high-pressure conditions incorporated with repeated mercury intrusion capillary pressure (MICP), and field emission-scanning electron microscopy (FE-SEM) imaging after Wood's metal (WM) impregnation were performed on overmature marine shale samples of the Wufeng-Longmaxi and Niutitang Formations from south China. Based on the electron micrographs of the WM-injected samples, it was found that the sealing of the pore system by brittle minerals is the root cause for a reduction in overall pore connectivity within the shale matrix. Aside from being favorable to the preservation of organic and clay mineral pores, brittle minerals however, resulted in the closure of pore network, thus, forming an isolated pore system. The novel approach of integrating repeated MICP measurement and FE-SEM imaging after WM impregnation provides a new evaluation method for pore-fracture connectivity of shale. The minimum fraction of pores within the overmature shales accessible to methane was at 38% and 78% within 100 nm. Moreover, because of confinement effects, the density of methane in a pore space less than 20 nm under high pressure was greater than that of an ideal gas under the same pressure conditions which even increased with decreasing of pore size to several times of its inert state and formed nanoscale methane clusters. The combination of contrast-matching SANS (CM-SANS) and repeated MICP measurements can effectively reveal the connectivity of pores within the matrix and the connectivity between such pores and microfractures, which helps to evaluate the distribution of closed pores and dominant transport spaces of gas in shale reservoirs. Overall, the pore-fracture connectivity in overmature marine shale controls the amount of gas that is supplied from matrix pores into fracture systems and also affects the density of the gas in pore spaces within the matrix.

Estimation of the Compositional Proportions of Different Micelle Species in Water: Application of One-dimensional Aggregate Theory to Small Angle Neutron Scattering Analyzed Data

Abstract The one-dimensional aggregation theory was applied to the small angle neutron scattering (SANS) analyzed data of surfactant solutions. Plots of the hydrophobic bonding energy E to form an aggregate against the number-average aggregation number n were found to be powerful to estimate the compositional ratios of different aggregate species co-existing in a gross sample solution.

Multiscale micro-architecture of pore space in rocks: size, shape, deformation and accessibility determined by small-angle neutron scattering (SANS)

A brief summary of the evolving applications of small-angle neutron scattering (SANS) to the microstructural research on geological materials in the last few decades is provided, including new developments and possible future directions. This is an account of authors’ view of the interplay between the technical development of SANS instrumentation, methodology and sample environments and the progress of research on the evolution of organic matter, gas adsorption and desorption, fluid transport in the pore space and the microstructure of rocks, based mostly on their own research interests.Graphical abstract

Influence of tail group length, amide functionality and added salt ion identity on the behaviour of betaine surfactants

HypothesisThe behaviour of surfactants in solution and at interfaces is governed by a combination of steric and electrostatic effects experienced by surfactant molecules as they interact with solvent, other species in solution, and each other. It would therefore be anticipated that highly interacting groups would significantly influence surfactant behaviour. The widely used amide functionality has polar H-bond donor/acceptor properties, and therefore its inclusion into a surfactant structure should have a profound effect on surface activity and self-assembly of that surfactant when compared to the equivalent molecule without an amide linker. Further, chaotropic or kosmotropic salt ions that affect water structuring and hydrogen bonding may provide opportunities for further tuning surfactant interactions in such cases.ExperimentsA library of betaine surfactant with tail lengths n=14−22 both with and without an amidopropyl linker were synthesised to study the effect of the amide functionality on surfactant properties. Characterisation of the molecules interfacial properties were performed using pendant drop tensiometry and their solution state formulation properties were probed using small-angle neutron scattering (SANS) and rheological measurements.FindingsPresence of an amidopropyl linker had little effect on aggregation propensity (as evidenced by critical micelle concentration) and aggregate morphology of betaine surfactants, but did increase the Krafft temperature of these surfactants. SANS analysis indicated that aggregate morphology of alkyl betaine surfactants could be influenced by the addition of sodium salts with chaotropic counterions (I− and SCN−), but they were insensitive to more kosmotropic anions (SO42−, F− and Cl−), providing unique and novel solution control methods for this (supposedly salt-insensitive) class of surfactants.

Equation Elucidating the Catalyst-Layer Proton Conductivity in a Polymer Electrolyte Fuel Cell Based on the Ionomer Distribution Determined Using Small-Angle Neutron Scattering.

The performance of a polymer electrolyte fuel cell can be enhanced by improving the proton conductivity of the catalyst layer, where the oxygen reduction reaction generates electrochemical power. Protons are conducted through the ionomer coatings on catalyst-supporting carbon particles, which form porous structures that facilitate oxygen diffusion during the reaction within the catalyst layer. Therefore, while a higher ionomer content in the catalyst layer is favorable, the proton conductivity is additionally governed by the type of carbon support. As the influence of the ionomer distribution is not fully understood, we introduce a novel proton conductivity model for use in simulating catalyst layers with various amounts of ionomers and different carbon types. This proton conductivity model considers that several ionomers occur as thin films with drastically suppressed proton conductivities. Although evaluating the thin-film ionomer fraction is challenging, proton-conducting ion clusters in thick-film ionomers have been detected by characterizing the catalyst layers via small-angle neutron scattering. Our model reveals that reducing the fraction of the thin-film ionomer or avoiding factors that suppress its proton conduction improves the performance of the catalyst layer.

Aqueous Binary Mixtures of Stearic Acid and Its Hydroxylated Counterpart 12-Hydroxystearic Acid: Fine Tuning of the Lamellar/Micelle Threshold Temperature Transition and of the Micelle Shape.

This study examines the structures of soft surfactant-based biomaterials which can be tuned by temperature. More precisely, investigated here is the behavior of stearic acid (SA) and 12-hydroxystearic acid (12-HSA) aqueous mixtures as a function of temperature and the 12-HSA/SA molar ratio (R). Whatever R is, the system exhibits a morphological transition at a given threshold temperature, from multilamellar self-assemblies at low temperature to small micelles at high temperature, as shown by a combination of transmittance measurements, Wide Angle X-ray diffraction (WAXS), small angle neutron scattering (SANS), and differential scanning calorimetry (DSC) experiments. The precise determination of the threshold temperature, which ranges between 20 °C and 50 °C depending on R, allows for the construction of the whole phase diagram of the system as a function of R. At high temperature, the micelles that are formed are oblate for pure SA solutions (R = 0) and prolate for pure 12-HSA solutions (R = 1). In the case of mixtures, there is a progressive continuous transition from oblate to prolate shapes when increasing R, with micelles that are almost purely spherical for R = 0.33.

The Future of Energy Storage: Detailed Description of Layered Structure and Porosity of Hard Carbons

The effort of commissioning green and renewable energy with the growing list of critical raw materials demands innovations in energy storage and conversion [1]. The research on sodium-ion batteries (SIBs) has proved promising for large-scale stationary energy storage. Therefore, the crucial need for material research for SIB applications has motivated the studies on hard carbon anodes that have shown high reversible capacity and low working potential[2]. Nevertheless, the exact sodium storage mechanism in hard carbons remains uncertain, inspiring the detailed study of the structure of non-graphitized carbons. Yet, the structure of hard carbons has no long-range order, which complicates the exact characterization. Thus, we present a study focusing on the chemically activated hard carbons' porous and graphite-like structures with complementary wide- and small-angle scattering methods (Figure 1). The current presentation examines the exact impact of the ratio of activating agents on the structure of hard carbons and how the structure affects the ability to store sodium ions. The studied materials were synthesized from D-glycose via hydrothermal carbonization and activated with zinc chloride with different ratios[3]. The evaluation of the layered structure of carbons from wide-angle x-ray scattering (WAXS) data was carried out with Ruland and Smarsly algorithm[4], which is more suitable for non-graphitic carbons than the typically used approaches. The porous structure was described with small-angle neutron scattering (SANS) data model-free analysis, combining Schiller, Mering, Perret, and Ruland approaches[5].This presentation reveals exciting results from the detailed data analysis that opens new perspectives to the material development for SIB hard carbon anodes. During activation of the hard carbon materials activated with zinc chloride with ratios 1:1.5 and 1:2 significant differences in the interlayer arrangement, pore sizes, and the degree of disorder appeared. The presented results indicate the role of different structural parameters on the charge-discharge plateau and sloping regions, guiding to the better understanding of the sodium storage mechanism in hard carbon anode. The presentation demonstrates the interpretation of the results with a focus on improving energy storage capability. It is discussed: is the detailed structural analysis for the non-graphitic carbons a comprehensive and new sight into the future of energy storage?[1] Critical Raw Materials for Strategic Technologies and Sectors in the EU A Foresight Study, (2020).[2] A. Adamson, R. Väli, M. Paalo, J. Aruväli, M. Koppel, R. Palm, E. Hark, J. Nerut, T. Romann, E. Lust, A. Jänes, Peat-Derived Hard Carbons for High Capacity Sodium-Ion Batteries: Synthesis and Characterization, ECS Meet. Abstr., MA2020-02 (2020) 78.[3] M. Härmas, T. Thomberg, A. Jänes, Effect of Zinc Chloride Activation on D-Glucose Derived Carbons Based Capacitors Performance in Ionic Liquid, J. Electrochem. Soc., 167 (2020) 080533.[4] W. Ruland, B. Smarsly, X-ray scattering of non-graphitic carbon: an improved method of evaluation, J. Appl. Crystallogr., 35 (2002) 624–633.[5] E. Härk, M. Ballauff, Carbonaceous Materials Investigated by Small-Angle X-ray and Neutron Scattering, C, 6 (2020) 82. Figure 1

Understanding Polymer Structure and Conductivity in Composite Electrolytes

Lithium ion batteries are a crucial technologies for electric vehicles and portable electronics due to their high energy density. However, flammable liquid electrolytes create a safety concern and transitioning to all solid state batteries allows for the potential of higher energy density by utilizing lithium metal anodes. Two classes of solid materials have been explored to replace liquid electrolytes: ceramic and polymer electrolytes. Composite electrolytes, typically in the form of dispersed ceramic particles or nanowires in polymer matrix, combine these two materials to have good ionic conductivity while maintaining the mechanical properties of the polymer. While they have achieved fairly high conductivity (typically 10-4 S/cm), the mechanism for such ion conduction is not well understood.The polymer likely plays a crucial role as the ceramic volume fractions are typically under 20%.1,2 Four possible ways that polymers could increase in conductivity in the composite have been identified: decreased crystallinity, increased free volume, disruption of polymer alignment, and increased lithium ion dissolution due to acidic surface groups on the ceramic.1,3,4 We have developed thin film model systems to probe the interface of the polymer with and ceramic surfaces. We found that when confined to thin films, the conductivity of the polymer electrolyte increased compared to the bulk. We utilized differential scanning calorimetry to identify the crystallinity and found that the small crystallinity variation could not account for the variation in conductivity. Subsequently, we utilized surface conductivity and transference number measurements to understand the effects of acidic surface groups. X-ray Absorption measurements will be similarly utilized to probe the variation in lithium ion environments within these materials to understand any variation in the lithium salt dissolution. It was found that the variation in conductivity based on this effect is small.In order to probe the possible variation in free volume, Small Angle Neutron Scattering will be utilized to quantify the free volume within thin films, bulk polymer, and composite electrolytes. This can quantify the volume associated with each monomer and therefore how much space is between polymer chains for lithium ion movement.5 Lastly, while the polymer chain alignment has not been extensively discussed composite literature, it has been identified that when polymer electrolytes are cast on a surface, polymer electrolytes typically show anisotropy with measurements parallel to the surface having higher conductivity due to the alignment of the chain.6 Therefore, ceramic fillers in the composites may disrupt this packing and allow for higher conductivity perpendicular to the cast surface, the direction in which they are most commonly measured. In order to probe this effect, we measure the anisotropy of both our thin film electrolytes as well as composite electrolytes to compare the significance of the anisotropy and utilize small angle x-ray scattering to measure any anisotropy in the structure.

Investigating the Impact of Hydrophobic Polymer Segments on the Self-Assembly Behavior of Supramolecular Cyclic Peptide Systems via Asymmetric-Flow Field Flow Fractionation.

The present study examines the behavior of cyclic peptide polymer conjugates that have been designed to combine their self-assembling ability via H-bonding with the properties of amphiphilic diblock copolymers. Using a combination of asymmetric flow-field flow fractionation (AF4) and small-angle neutron scattering (SANS), we have uncovered unique insight based on the population of structures established at a 24 h equilibrium profile. Our results determine that by introducing a small quantity of hydrophobicity into the conjugated polymer corona, the resulting nanotube structures exhibit low unimer dissociation which signifies enhanced stability. Furthermore, as the hydrophobicity of the polymer corona is increased, the elongation of the nanotubes is observed due to an increase in the association of unimers. This encompasses not only the H-bonding of unimers into nanotubes but also the self-assembly of single nanotubes into segmented-nanotube structures with high aspect ratios. However, this influence relies on a subtle balance between the hydrophobicity and hydrophilicity of the polymer corona. This balance is proposed to determine the solvent entropic penalty of hydrating the system, whereby the cost scales with the hydrophobic quantity. Consequently, it has been suggested that at a critical hydrophobic quantity, the solvation penalty becomes high enough such that the self-assembly of the system deviates from ordered hydrogen bonding. The association behavior is instead dominated by the hydrophobic effect which results in the undesirable formation of disordered aggregates.

Shear influence on colloidal cluster growth: a SANS and USANS study.

This study examines the time evolution of silica/water clusters where the formation of a gel network from unitary silica particles is interrupted by a simple Couette shear field. The aim is to enable the general understanding of this simple system by examining the microscopic basis for the changes in viscosity by providing structural inputs from small-angle scattering for a simple theoretical model. The experimental system is an 8.3 nm particle silica solution (Ludox) where the gelation has been initiated by lowering the pH in a Couette cell providing a constant shear rate of 250 s-1. A unified small-angle neutron scattering (SANS) and ultra-small-angle neutron scattering (USANS) procedure is described to measure the scattered intensity in a wavevector range of 3 × 10-4 ≤ q (nm-1) ≤ 3.1 × 10-1, probing structural changes over a broad range of length scales from the nanometre to the micrometre. Scattering data provide a new means of better understanding the behaviour of colloidal clusters when subjected to an external applied shear over a continuous time sequence after gel initiation; a fit of the time-dependent scattered intensity leads to an estimation of the cluster's effective volume fraction and size as a function of time. A reductionist theoretical basis is described to predict the time-dependent viscosity behaviour of the sheared colloidal suspension gel-initiated cluster growth from the volume fraction of the clusters.

Effect of temperature on the conformation and functionality of poly(N-isopropylacrylamide) (PNIPAM)-grafted nanocellulose hydrogels

HypothesisPoly(N-isopropylacrylamide) [PNIPAM]-grafted cellulose nanofibers (CNFs) are new thermo-responsive hydrogels which can be used for a wide range of applications. Currently, there is no clear understanding of the precise mechanism by which CNFs and PNIPAM interact together. Here, we hypothesize that the physical crosslinking of grafted PNIPAM on CNF inhibits the free movement of individual CNF, which increases the gel strength while sustaining its thermo-responsive properties. ExperimentsThe thermo-responsive behaviour of PNIPAM-grafted CNFs (PNIPAM-g-CNFs), synthesized via silver-catalyzed decarboxylative radical polymerization, and PNIPAM-blended CNFs (PNIPAM-b-CNFs) was studied. Small angle neutron scattering (SANS) combined with Ultra-SANS (USANS) revealed the nano to microscale conformation changes of these polymer hybrids as a function of temperature. The effect of temperature on the optical and viscoelastic properties of hydrogels was also investigated. FindingsGrafting PNIPAM from CNFs shifted the lower critical solution temperature (LCST) from 32 °C to 36 °C. Below LCST, the PNIPAM chains in PNIPAM-g-CNF sustain an open conformation and poor interaction with CNF, and exhibit water-like behaviour. At and above LCST, the PNIPAM chains change conformation to entangle and aggregate nearby CNFs. Large voids are formed in solution between the aggregated PNIPAM-CNF walls. In comparison, PNIPAM-b-CNF sustains liquid-like behaviour below LCST. At and above LCST, the blended PNIPAM phase separates from CNF to form large aggregates which do not affect CNF network and thus PNIPAM-b-CNF demonstrates low viscosity. Understanding of temperature-dependent conformation of PNIPAM-g-CNFs engineer thermo-responsive hydrogels for biomedical and functional applications.

Time-Resolved Structural Analysis of Fast-Photoresponsive Surfactant Micelles by Stroboscopic Small-Angle Neutron Scattering.

Photoresponsive materials are garnering attention because of their applications toward building a sustainable society. A recently developed fast-photoresponsive amphiphilic lophine dimer (3TEG-LPD) responds rapidly to light, making it a promising candidate for drug-delivery systems. In this study, the mechanism of structural changes induced by ultraviolet (UV) irradiation in 3TEG-LPD micelles in an aqueous solution was investigated via an in situ time-resolved small-angle neutron scattering (SANS) technique. Since subsecond resolution was necessary to observe the structural changes in the 3TEG-LPD micelles, stroboscopic SANS analysis was employed to obtain scattering profiles with a time width of 0.5 s. The structural parameters were quantitatively determined by performing a model-fitting analysis of the SANS results. The stroboscopic SANS results showed that upon UV irradiation, the axial ratio and pseudo-aggregation number of the 3TEG-LPD micelles increased by 1.8 and 1.6 times, respectively, whereas the number of water molecules per surfactant molecule decreased. This finding suggested that the change in the shape of the micelles from spherical to ellipsoidal shape was accompanied by dehydration. Under the present UV irradiation conditions, this structural change of the micelle occurred rapidly during the first 30 s after the start of UV irradiation. Each structural parameter recovered exponentially and reversibly during the recovery process after the cessation of UV irradiation. The changes in these parameters were analyzed in terms of kinetics by comparing them with the changes in the molecular structure. We found that the change of the micelles proceeds approximately twice as fast as the association of the molecule. Furthermore, from the perspective of the critical packing parameter consideration, the SANS analysis revealed that the UV-induced changes in 3TEG-LPD micelles are dominated by the enthalpy contribution. This finding is expected to be useful for developing new materials for various applications.

Polarized Neutrons Observed Nanometer-Thick Crystalline Ice Plates in Frozen Glucose Solution.

Spin-contrast-variation (SCV) small-angle neutron scattering (SANS) is a technique to determine the nanostructure of composite materials from the scattering of polarized neutrons that changes with proton polarization of samples. The SCV-SANS enabled us to determine structure of nanoice crystals that were generated in rapidly frozen sugar solutions by separating the overlapped signals from the nanoice crystals and frozen amorphous solutions. In the frozen glucose solution, we found that the nanoice crystals formed a planar structure with a radius larger than several tens of nanometers and a thickness of 2.5 ± 0.5 nm, which was close to the critical nucleation size of ice crystals in supercooled water. This result suggests that the glucose molecules were preferentially bound to a specific face of nanoice crystals and then blocked the crystal growth perpendicular to that face.

Microscopic Analysis of the Water/Glycerol/EO30PS System in Bulk and on a Solid Substrate.

Surfactant systems are often employed in cosmetic formulations where they dry on skin as a surface, thereby becoming increasingly concentrated systems. To better understand this drying process, we focused on the difference of self-assembled structures of the water/glycerol/polyoxyethylene (30) phytosteryl ether (EO30PS) system in bulk and on a solid substrate because the interaction between the substrate and the surfactant may have a substantial effect on the self-assembly, which may be related to the bulk structure but in detail may also differ strongly from the bulk situation. In bulk, small-angle neutron scattering (SANS) experiments showed that with increasing loss of water, the degree of ordering increases but changes of the aggregate structure are rather small. The results indicate that ellipsoidal micelles of EO30PS are densely packed and simply become more ordered in bulk during the drying process. On the other hand, neutron reflectometry revealed that EO30PS molecules adsorb onto a Si surface in the form of bilayers and analysis indicates that at a high concentration (c = 20 wt %), there are on average two bilayers (a double bilayer) on the Si substrate. The adsorbed membrane structure of EO30PS is rather thin with respect to its hydrophobic part, indicating tilted molecules, containing only some solvent, and being not highly ordered. These experimental results then allow for a much deeper understanding of the structural properties of practical formulations as they are applied, for instance, in cosmetic lotions.